Fast living cationic polymerization of vinyl ethers with iron(III) chloride in the presence of a cyclic ether: Most active and environmentally benign catalyst for the living cationic polymerization of vinyl ethers

Kanazawa, Arihiro; Hirabaru, Yumi; Kanaoka, Shokyoku; Aoshima, Sadahito

doi:10.1002/pola.21632

Cited by 42 publications

(34 citation statements)

References 29 publications

(13 reference statements)

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“…3), and a polymer with a very narrow MWD was obtained (M w /M n ¼ 1.06). 27 The M n values of these polymers increased in direct proportion to the monomer conversion, and their MWDs were very narrow during the polymerization (M w /M n 1.1). These results all supported the occurrence of fast living cationic polymerization with FeCl 3 .…”

Section: Various Lewis Acid Catalysts For Living Cationic Polymerizatmentioning

confidence: 96%

“…During such investigations, we quite recently developed ultrafast living polymerizations 25,26 and more environmentally friendly initiating systems. 27,28 These findings encouraged a reexamination of this area specifically focusing on the feasibility of living polymerization with a variety of Lewis acids. This article summarizes the results of these recent advances.…”

Section: Introductionmentioning

confidence: 99%

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New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Aoshima

Yoshida

Kanazawa

et al. 2007

J. Polym. Sci. A Polym. Chem.

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Our recent extensive research on Lewis acid catalysts with a weak base for the cationic polymerization of vinyl ethers led to unprecedented living reaction systems: fast living polymerization within 1-3 s; a wide choice of metal halides containing Al, Sn, Fe, Ti, Zr, Hf, Zn, Ga, In, Si, Ge, and Bi; and heterogeneously catalyzed living polymerization with Fe 2 O 3 . The use of added bases for the stabilization of the propagating carbocation and the appropriate selection of Lewis acid catalysts were crucial to the success of such new types of living polymerizations. In addition, the base-stabilized living polymerization allowed the quantitative synthesis of star-shaped polymers with a narrow molecular weight distribution via polymerlinking reactions and the precision synthesis and self-assembly of stimuli-responsive block copolymers.

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Section: Various Lewis Acid Catalysts For Living Cationic Polymerizatmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Aoshima

Yoshida

Kanazawa

et al. 2007

J. Polym. Sci. A Polym. Chem.

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“…In contrast, SnCl 4 , FeCl 3 and GaCl 3 , which have more chloride affinity, 22,30 would remove the Cl atom from IBVE-HCl, generating a carbocation with the structure derived from IBVE for inducing copolymerization. Thus, copolymerization was conducted in toluene at À78 C using SnCl 4 , FeCl 3 , and GaCl 3 ( Table 1, entries 5-7, respectively), which showed different interactions 22,35,36 With all acids, polymers were produced in addition to the cyclic trimer. GPC profiles of the products showed strong UV absorptions, detected at 254 nm, corresponding to the RI counterparts, indicating that the polymers contained BzA evenly over the entire molecular weight region.…”

Section: Copolymerization Of Bza With Ibve Using Various Lewis Acidsmentioning

confidence: 99%

“…On the other hand, our previous studies demonstrated that an appropriate initiator as a cationogen varied among Lewis acids. For example, the adduct of IBVE with acetic acid (IBEA) and sulfonic acid is an effective initiator for an Al based acid; 18,37 IBVE-HCl and alkyl halides for SnCl 4 , FeCl 3 , and GaCl 3 ; 35,36,38 and acetal, alkyl alkoxides, and alkyl halides for TiCl 4 . [39][40][41] The central metal of GaCl 3 , which showed the highest catalytic activity on copolymerization, is an element of Group 13 as is Al.…”

Section: Controlled Copolymerization Using Ethanesulfonic Acid As An mentioning

confidence: 99%

Controlled cationic copolymerization of benzaldehyde with isobutyl vinyl ether using base‐assisting system

Ishido

Aburaki

Kanaoka

et al. 2010

J. Polym. Sci. A Polym. Chem.

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Well‐controlled cationic copolymerization of benzaldehyde with IBVE was achieved using ethanesulfonic acid as an initiator in conjunction with GaCl3 in the presence of an added base. Copolymerization proceeded smoothly in toluene at −78 °C, yielding copolymers with very low polydispersity (Mw/Mn ∼ 1.1). Reactive conditions are critical for successful copolymerization: Every single parameter and ingredient is indispensable. For example, only homopolymerization of IBVE occurred in CH2Cl2 or in the absence of an added base.

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“…However, recently fast living cationic polymerization systems that completed in seconds were obtained using IBEA-Et x AlCl 3-x / SnCl 4 /base or IBVE-HCl/FeCl 3 /cyclic ether combinations. [6][7][8] The polymerization rates were thousands of times larger than that using EtAlCl 2 alone, a catalyst commonly used for an added base system, and were also significantly larger than those of other initiating systems. The balance between the acidity of the Lewis acid and the basicity of the added base is the key to achieving such acceleration without loss of the livingness.…”

Section: Introductionmentioning

confidence: 99%

Major Progress in Catalysts for Living Cationic Polymerization of Isobutyl Vinyl Ether: Effectiveness of a Variety of Conventional Metal Halides

2009

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Cationic polymerization of isobutyl vinyl ether (IBVE) was examined using a variety of metal halides. In the presence of an appropriate added base, ester or ether, the living polymerization of IBVE proceeded for almost all Lewis acids (MCl n ; M: Fe, Ga, Sn, In, Zn, Al, Hf, Zr, Bi, Ti, Si, Ge, Sb) used in conjunction with an IBVE-HCl adduct in toluene at 0°C. The difference in the polymerization activity of these Lewis acids was significant. As examples, polymerization with some acids, such as FeCl 3 , proceeded in the order of seconds, whereas it took more than a few weeks with others such as SiCl 4 and GeCl 4 . The difference in activity is based on the strength of the interaction between the Lewis acid and the propagating end chloride anion and/or the basic carbonyl (or ether) oxygen atom of the added base, that is, the chlorophilic or oxophilic nature of each metal halide is a decisive factor. In addition, a suitable combination of a Lewis acid and an additive was indispensable for living polymerization. With metal pentachlorides, NbCl 5 and TaCl 5 , addition of a salt (nBu 4 NCl) resulted in superior control of the reaction over that for addition of a base. Lewis acids for living cationic polymerization of vinyl ether were categorized into groups depending on the preferences for these additives.

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Fast living cationic polymerization of vinyl ethers with iron(III) chloride in the presence of a cyclic ether: Most active and environmentally benign catalyst for the living cationic polymerization of vinyl ethers

Cited by 42 publications

References 29 publications

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Controlled cationic copolymerization of benzaldehyde with isobutyl vinyl ether using base‐assisting system

Major Progress in Catalysts for Living Cationic Polymerization of Isobutyl Vinyl Ether: Effectiveness of a Variety of Conventional Metal Halides

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